Use of sunscreen combinations which comprise, as essential constituent, 2-(4-alkoxyanilinomethylene) malonic dialkyl esters as photostable UV filters in cosmetic and pharmaceutical preparations

ABSTRACT

Use of sunscreen combinations which comprise, as essential constituent, 2-(4-alkoxyanilinomethylene)malonic dialkyl esters as photostable UV filters in cosmetic and pharmaceutical preparations 
     A) compound absorbing essentially in the UV-A region and 
     B) further compounds absorbing in the UV-A region, in the UV-B region and over both regions, 
      where the constituent absorbing in the UV-A region consists of 
     A) effective amounts of at least one of the compounds of the formula I                    
      in which the substituents R 1  to R 3 , independently of one another, are C 1 -C 8 -alkyl 
     as photostable UV filters in cosmetic and pharmaceutical preparations for protecting human skin and human hair against solar rays.

Use of sunscreen combinations which comprise, as essential constituent,2-(4-alkoxyanilinomethylene)malonic dialkyl esters as photostable UVfilters in cosmetic and pharmaceutical preparations

The invention relates to the use of sunscreen combinations whichcomprise, as essential constituent, the2-(4-alkoxyanilinomethylene)malonic dialkyl esters which absorb in theUV-A region, and at least one further sunscreen which absorbs in theUV-A region, UV-B region or in both regions, chosen from a group definedin detail below as photostable UV filter combination in cosmetic andpharmaceutical preparations for protecting the human epidermis or humanhair against UV radiation, specifically in the range from 320 to 400 nm.

The sunscreens employed in cosmetic and pharmaceutical preparations havethe task of preventing, or at least diminishing the consequences of,harmful effects of sunlight on the human skin. However, these sunscreensalso serve to protect other ingredients from decomposition ordegradation by UV radiation. In hair cosmetic formulations the aim is toreduce damage to the keratin fibers by UV rays.

The sunlight reaching the surface of the earth contains proportions ofUV-B radiation (280 to 320 nm) and UV-A radiation (>320 nm), which aredirectly adjacent to the visible light region. The effect on the humanskin is manifested, particularly in the case of UV-B radiation, bysunburn. Accordingly, the industry offers a relatively large number ofsubstances which absorb UV-B radiation and thus prevent sunburn.

Dermatological investigations have now shown that UV-A radiation is alsoperfectly capable of causing skin damage and allergies by, for example,damaging the keratin or elastin. This reduces the elasticity and waterstorage capacity of the skin, i.e. the skin becomes less supple andtends to form wrinkles. The noticeably high incidence of skin cancer inregions where the sun's radiation is strong shows that damage to thegenetic information in the cells is evidently also caused by sunlight,specifically by UV-A radiation. All these findings would thereforesuggest the need to develop efficient filter substances for the UV-Aregion.

There is a growing demand for sunscreens for cosmetic and pharmaceuticalpreparations which can be used in particular as UV-A filters and whoseabsorption maxima ought therefore to be in the range from about 320 to380 nm. In order to achieve the required effect using the minimumamount, sunscreens of this type ought additionally to have a highspecific absorbance. Sunscreens for cosmetic products must also meet alarge number of other requirements, for example good solubility incosmetic oils, high stability of the emulsions produced with them,toxicological acceptability, and low intrinsic odor and low intrinsiccolor.

Another requirement which sunscreens must meet is adequatephotostability. However, this is only inadequately ensured, if at all,with the UV-A-absorbing sunscreens hitherto available.

French Patent No. 2 440 933 describes4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane as a UV-A filter. It isproposed to combine this specific UV-A filter, which is sold by GIVAUDANunder the name “PARSOL 1789”, with various UV-B filters in order toabsorb all UV rays having a wavelength from 280 to 380 nm.

However, this UV-A filter does not have sufficient photochemicalstability, when used alone or in combination with UV-B filters, toensure sustained protection of the skin during sunbathing for prolongedperiods, which means that repeated applications at regular and shortintervals are required if effective protection of the skin from all UVrays is desired.

For this reason, EP-A-0 514 491 discloses the stabilization of theinsufficiently photostable UV-A filters by adding2-cyano-3,3-diphenylacrylic esters which themselves act as filters inthe UV-B region.

It has furthermore already been proposed in EP-A-0 251 398 and EP-A-0416 837 to combine chromophores absorbing UV-A radiation and UV-Bradiation into one molecule using a linker. This has the disadvantagethat firstly a free combination of UV-A and UV-B filters in the cosmeticpreparation is no longer possible, and that difficulties in the chemicallinkage of the chromophores allow only certain combinations.

It is an object of the present invention to propose sunscreens forcosmetic and pharmaceutical purposes which absorb in the UV-A regionwith high absorbance, which are photostable, have low intrinsic color,i.e. a sharp band structure, and are soluble in oil or water dependingon the substituent.

We have found that this object can be achieved advantageously by certainsunscreen combinations.

Accordingly, this object is achieved according to the invention by theuse of sunscreen combinations comprising a

A) compound absorbing essentially in the UV-A region and

B) further compounds absorbing in the UV-A region, in the UV-B regionand over both regions,

 where the constituent absorbing in the UV-A region consists of

A) effective amounts of at least one of the compounds of the formula I

 in which the substituents R¹ to R³, independently of one another, areC₁-C₈-alkyl and the constituent

B) comprises effective amounts of one or more compounds chosen from thegroup consisting of

Ba) hydroxybenzophenones of the formula II

 in which the substituents, independently of one another, have thefollowing meanings:

R⁴ and R⁵

are hydrogen, C₁-C₁₂-alkyl, C₃-C₁₀-cycloalkyl, where the substituents R⁴and R₅ may, together with the nitrogen atom to which they are bonded,form a 5- or 6-membered ring and

R⁶ hydrogen, C₁-C₁₂-alkyl, C₃-C₁₀-cycloalkyl;

Bb) diarylbutadienes of the formula III

 in which the substituents R⁷ and R⁸, independently of one another, maybe hydrogen, C₁-C₁₂-alkyl or C₃-C₁₀-cycloalkyl,

Bc) the compound of the formula IV

Bd) the compound of the formula V

Be) the compound of the formula VI

Bf) the compound of the formula VII

Bg) an organosiloxane benzalmalonate of the formula VIIIa

 in which

V₁′ is the group

V₁ is a methyl group or V₁′, or of the formula VIIIb

 in which V₂′ is the group of the structure

V₂ is a methyl group or V₂′

or mixtures of compounds of the formulae VIIIa and VIIIb,

where t is a value up to 100 and u is a value up to 20, with the provisothat u=0 when V₁=V₁′ and/or V₂=V₂′, and u is a value from 1 to 20 whenV₁=CH₃ and/or V₂=CH₃,

Bh) the compound of the formula IX

Bi) the compound of the formula X

Bj) the compound of the formula XI

 in which X is hydrogen, sodium, potassium, ammonium ortriethanolammonium,

Bk) the compound of the formula XII

 as photostable UV filters in cosmetic and pharmaceutical preparationsfor protecting human skin or human hair against UV rays, in particularagainst natural solar rays, optionally together with further compoundswhich absorb in the UV region and which are known per se for cosmeticand pharmaceutical preparations.

Alkyl radicals R¹ to R³ in compound I which may be mentioned arebranched or unbranched C₁-C₈-alkyl chains, preferably methyl, ethyl,n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl,1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethyl-1methylpropyl, 1-ethyl-2-methylpropyl,n-heptyl or n-octyl. Preferred radicals for R¹ to R³ are methyl, ethyl,n-propyl and 1-methylethyl.

Alkyl radicals R⁴, R⁵ and R⁶ in compound II which may be mentioned arebranched or unbranched C₁-C₁₂-alkyl chains, preferably methyl, ethyl,n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl,1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl,n-heptyl, n-octyl or 2-thylhexyl.

Particularly preferred alkyl radicals which may be mentioned for R⁴, R⁵and R⁶ are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl,1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl,2-ethylhexyl.

Alkyl radicals R⁷ and R⁸ in compound III which may be mentioned arebranched or unbranched C₁-C₁₂-alkyl chains, preferably methyl, ethyl,n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl,1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl,n-heptyl, n-octyl or 2-ethylhexyl.

Particularly preferred alkyl radicals which may be mentioned for R⁷ andR⁸ are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl,2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 2-ethylhexyl.

Cycloalkyl radicals which may be mentioned for R⁴ to R⁸ in formulae IIand III are preferably branched or unbranched C₃-C₁₀-cycloalkyl chains,such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,1-methylcyclopropyl, 1-ethylcyclopropyl, 1-propylcyclopropyl,1-butylcyclopropyl, 1-pentylcyclopropyl, 1-methyl-1-butylcyclopropyl,1,2-dimethylcyclopropyl, 1-methyl-2-ethylcyclopropyl, cyclooctyl,cyclononyl or cyclodecyl.

Particularly preferred cycloalkyl radicals for R⁴ to R⁸ which may bementioned are C₃-C₆-cycloalkyl radicals, very particularly preferablycyclopropyl, cyclopentyl and cyclohexyl.

The sunscreen combination of the compounds (A) and (B) can be used aloneor in combination with further compounds which absorb in the UV region,although at least effective amounts of the compounds (A) and (B) shouldbe present in the sunscreen preparations. Effective amounts of thecompounds (A) and of the compounds (B) is generally to be understood asmeaning in each case at least 0.1% by weight, in each case based on thecosmetic preparation.

In the sunscreen combinations according to invention, the amount ofcompounds which absorb in the UV-B region usually predominates.Accordingly, the content of the compound (A) which absorbs in the UV-Aregion is generally 5 to 50% by weight, preferably 10 to 25% by weight,in each case based on a sunscreen combination of (A) and (B).

The sunscreen combinations are characterized by their highphotostability, and the preparations prepared with the sunscreencombinations are characterized by their pleasant feel on the skin. Thesun protection factors achieved with the combinations are considerablyhigher than the additive values of the individual UV filters. Even theUV-A protection performance of the sunscreen combinations according tothe invention—with regard to the critical wavelength, the PPD value(persistent pigment darkening), the IPD value (immediate pigmentdarkening), and the UVA/UVB ratio—is higher than that which can beachieved by the known UV filters according to the prior art.

The compound of the formula I is described in U.S. Pat. No. 6,069,170 asa constituent of cosmetic preparations. Moreover, in column 3 of saidpatent, lines 5 to 27, it is mentioned that it is possible to use thecompound group to which the compound of the formula I belongs togetherwith known ultraviolet absorbers. However, from this information it wasnot possible to conclude that particularly advantageous combinations canbe obtained with certain selected UV absorbers.

The compounds (B) are all known and are characterized in more detailbelow:

Ba) The compound of the formula II is known from EP-A-1 046 391.

Bb) The compound of the formula III is known from EP-A-0 916335.

Bc) The compound of the formula IV has the CAS No. 88122-99-0 and issold under the trade name Uvinul® T150 (BASF).

Bd) The compound of the formula V has the CAS No. 187393-00-6.

Be) The compound of the formula VI has the CAS No. 103597-45-1 and issold under the trade name Tinosorb® M (CIBA).

Bf) The compound of the formula VII has the CAS No. 155633-54-8 and isknown under the trade name Mexoryl® XL (CHIMEX).

Bg) The compounds or mixtures of compounds of the formula VIII are knownfrom EP-A 0920859. Of the compounds of the formulae VIIIa and/or VIIIb,those with the CAS numbers 208391-15-5, 208391-15-5D, 177955-90-7,177955-90-7 D and 177995-90-7DP are particularly suitable.

Bh) The compound of the formula IX has the CAS No. 154702-15-5 and issold under the trade name Uvasorb® HEB (BV Sigma).

Bi) The compound of the formula X has the CAS No. 6197-30-4 and is soldunder the trade name Uvinul® N539 (BASF).

Bj) The compound of the formula XI has the CAS No. 180898-37-7 (Haarmann& Reimer).

Bk) The compound of the formula XII has the CAS No. 131-55-5 and is soldunder the trade name Uvinul® D50 (BASF).

In the sunscreen combinations to be used according to the invention, itis possible for not only individual compounds (Ba) to (Bk) to bepresent, but also mixtures of two or more of these compounds.

The present invention further provides cosmetic and pharmaceuticalpreparations which have 0.1 to 40% by weight, preferably 1 to 25% byweight, based on the total amount of the cosmetic and pharmaceuticalpreparation, of a sunscreen combination comprising a

A) compound absorbing essentially in the UV-A region and

B) further compounds absorbing in the UV-A region, in the UV-B regionand over both regions,

 where the constituent absorbing in the UV-A region consists of

A) effective amounts of the compound of the formula I

 and the constituent

B) comprises effective amounts of one or more compounds chosen from thegroup consisting of

Ba) hydroxybenzophenone of the formula IIa

Bb) diarylbutadiene of the formula IIIa

Bc) the compound of the formula IV

Bd) the compound of the formula V

Be) the compound of the formula VI

Bf) the compound of the formula VII

Bg) an organosiloxane benzalmalonate of the formula VIIIa

 in which

V₁′ is the group

V₁ is a methyl group or V₁′, or of the formula VIIIb

 in which V₂′ is the group of the structure

V₂ is a methyl group or V₂′

or mixtures of compounds of the formulae VIIIa and VIIIb,

where t is a value up to 100 and u is a value up to 20, with the provisothat u=0 when V₁=V₁′ and/or V₂=V₂′, and u is a value from 1 to 20 whenV₁=CH₃ and/or V₂=CH₃,

Bh) the compound of the formula IX

Bi) the compound of the formula X

Bj) the compound of the formula XI

 in which X is hydrogen, sodium, potassium, ammonium ortriethanolammonium,

Bk) the compound of the formula XII

optionally together with further compounds which absorb in theUV-A-region and UV-B-region and which are known per se for cosmetic andpharmaceutical preparations, where the UV-A-absorbing compounds areusually used in a lesser amount than the UV-B-absorbing compounds.

The sunscreen-containing cosmetic and pharmaceutical preparations are,as a rule, based on a carrier which comprises at least one oil phase.However, preparations based solely on water are also possible ifcompounds having hydrophilic substituents are used. Accordingly, oils,oil-in-water and water-in-oil emulsions, creams and pastes,lip-protection stick compositions or non-greasy gels are suitable.

Suitable emulsions are inter alia also O/W macroemulsions, O/Wmicroemulsions or O/W/O emulsions containing the compound of the formulaI in dispersed form, the emulsions being obtainable by phase inversiontechnology, as in DE-A-197 26 121. Here, the particle size of thecompound of the formula I is chosen such that it is 3 μm or less,preferably 1 μm or less than the average particle size.

Conventional cosmetic auxiliaries which may be suitable as additivesare, for example, coemulsifiers, fats and waxes, stabilizers,thickeners, biogenic active substances, film formers, fragrances, dyes,pearlizing agents, preservatives, pigments, electrolytes (e.g. magnesiumsulfate) and pH regulators. Suitable and preferred coemulsifiers areknown W/O and also O/W emulsifiers such as polyglycerol esters, sorbitanesters or partially esterified glycerides. Typical examples of fats areglycerides; waxes which may be mentioned are, inter alia, beeswax,paraffin wax or microwaxes, possibly combined with hydrophilic waxes.Stabilizers which can be employed are metal salts of fatty acids suchas, for example, magnesium stearate, aluminum stearate and/or zincstearate. Examples of suitable thickeners are crosslinked polyacrylicacids and derivatives thereof, polysaccharides, in particular xanthangum, guar guar, agar agar, alginates and tyloses, carboxymethylcelluloseand hydroxyethylcellulose, also fatty alcohols, monoglycerides and fattyacids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone.Examples of biogenic active ingredients are plant extracts, proteinhydrolysates and vitamin complexes. Examples of customary film formersare hydrocolloids such as chitosan, microcrystalline chitosan orquaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinylacetate copolymers, polymers of the acrylic acid series, quaternarycellulose derivatives and similar compounds. Examples of suitablepreservatives are formaldehyde solution, p-hydroxybenzoate or sorbicacid. Examples of suitable pearlizing agents are glycol distearic esterssuch as ethylene glycol distearate, but also fatty acids and fatty acidmonoglycol esters. Dyes which can be used are the substances suitableand approved for cosmetic purposes, as listed, for example, in thepublication “Kosmetische Färbemittel” [Cosmetic Colorants] from theFarbstoffkommission der Deutschen Forschungsgemeinschaft [Dyescommission of the German Research Society], published by Verlag Chemie,Weinheim, 1984. These dyes are normally used in a concentration of from0.001 to 0.1% by weight, based on the total mixture.

An additional content of antioxidants is generally preferred. Thus, itis possible to use as favorable antioxidants all antioxidants which arecustomary or suitable for cosmetic and/or dermatological applications.

The antioxidants are advantageously chosen from the group consisting ofamino acids (e.g. glycine, histidine, tyrosine, tryptophan) andderivatives thereof, imidazoles (e.g. urocanic acid) and derivativesthereof, peptides such as D,L-carnosine, D-carnosine, L-carnosine andderivatives thereof (e.g. anserine), carotenoids, carotenes (e.g.β-carotene, lycopene) and derivatives thereof, chlorogenic acid andderivatives thereof, lipoic acid and derivatives thereof (e.g.dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols(e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and theglycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, and lauryl,palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters thereof)and salts thereof, dilauryl thiodipropionate, distearylthiodipropionate, thiodipropionic acid and derivatives thereof (esters,ethers, peptides, lipids, nucleotides, nucleosides and salts), andsulfoximine compounds (e.g. buthionine sulfoximines, homocysteinesulfoximines, buthionine sulfones, penta-, hexa-, heptathioninesulfoximine) in very low tolerated doses (e.g. pmol to μmmol/kg), andalso (metal) chelating agents (e.g. α-hydroxy fatty acids, palmiticacid, phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid,lactic acid, malic acid), humic acid, bile acid, bile extracts,bilirubin, biliverdin, EDTA and derivatives thereof, unsaturated fattyacids and derivatives thereof (e.g. γ-linolenic acid, linoleic acid,oleic acid), folic acid and derivatives thereof, ubiquinone andubiquinol and derivatives thereof, vitamin C and derivatives thereof(e.g. ascorbyl palmitate, Mg ascorbylphosphate, ascorbylacetate),tocopherol and derivatives (e.g. vitamin E acetate, tocotrienol),vitamin A and derivatives (vitamin A palmitate), and coniferyl benzoateof benzoin resin, rutinic acid and derivatives thereof, α-glycosylrutin,ferulic acid, furfurylideneglucitol, carnosine, butylhydroxytoluene,butylhydroxyanisole, nordihydroguaiacic acid, nordihydroguaiaretic acid,trihydroxybutyrophenone, uric acid and derivatives thereof, mannose andderivatives thereof, zinc and derivatives thereof (e.g. ZnO, ZnSO₄),selenium and derivatives thereof (e.g. selenomethionine), stilbenes andderivatives thereof (e.g. stilbene oxide, trans-stilbene oxide).

The amount of the abovementioned antioxidants (one or more compounds) inthe preparations is preferably from 0.001 to 30% by weight, particularlypreferably from 0.05 to 20% by weight, in particular from 1 to 10% byweight, based on the total weight of the preparation.

If vitamin E and/or derivatives thereof are used as the antioxidant(s),it is advantageous to choose their particular concentration from therange 0.001 to 10% by weight, based on the total weight of theformulation.

If vitamin A and/or derivatives thereof, or carotenoids are theantioxidant(s), it is advantageous to choose their particularconcentration from the range 0.001 to 10% by weight, based on the totalweight of the formulation.

Customary oil components in cosmetics are, for example, paraffin oil,glyceryl stearate, isopropyl myristate, diisopropyl adipate,cetylstearyl 2-ethylhexanoate, hydrogenated polyisobutene, vaseline,caprylic/capric triglycerides, microcrystalline wax, lanolin and stearicacid.

The total amount of auxiliaries and additives can be from 1 to 80% byweight, preferably from 6 to 40% by weight, and the nonaqueous fraction(“active substance”) can be from 20 to 80% by weight, preferably from 30to 70% by weight, based on the compositions. The compositions can beprepared in a manner known per se, i.e. for example by hot, cold,hot-hot/cold or PIT emulsification. This is a purely mechanical process;no chemical reaction takes place.

Such sunscreen preparations can accordingly be in liquid, paste or solidform, for example as water-in-oil creams, oil-in-water creams andlotions, aerosol foam creams, gels, oils, marking pencils, powders,sprays or alcoholic-aqueous lotions.

Finally, it is also possible to co-use further substances which absorbin the UV region and are known per se provided they are stable in theoverall system of the combination of UV filters to be used according tothe invention.

Suitable UV filter substances which can be additionally used with thesunscreen combinations to be used according to the invention are anyUV-A and UV-B filter substances. Examples which may be mentioned are:

CAS No. No. Substance (=acid) 1 4-Aminobenzoic acid 150-13-0 23-(4′-Trimethylammonium)benzylidenbornan-2-one 52793-97-2 methylsulfate3 3,3,5-Trimethylcyclohexyl salicylate 118-56-9 (homosalate) 42-Hydroxy-4-methoxybenzophenone 131-57-7 (oxybenzone) 52-Phenylbenzimidazole-5-sulfonic acid and its 27503-81-7 potassium,sodium and triethanolamine salts 63,3′-(1,4-Phenylenedimethine)-bis(7,7-dimethyl- 90457-82-22-oxobicyclo[2.2.1]heptane-1-methanesulfonic acid) and its salts 7Polyethoxyethyl 4-bis(polyethoxy)aminobenzoate 113010-52-9 82-Ethylhexyl 4-dimethylaminobenzoate 21245-02-3 9 2-Ethylhexylsalicylate 118-60-5 10 2-Ethylhexyl 4-methoxycinnamate 5466-77-3 112-Hydroxy-4-methoxybenzophenone-5-sulfonic acid 4065-45-6(sulisobenzone) and the sodium salt 123-(4′-Sulfo)benzylidenebornan-2-one and salts 58030-58-6 133-Benzylidenebornan-2-one 16087-24-8 141-(4′-Isopropylphenyl)-3-phenylpropane- 63260-25-9 1,3-dione 154-Isopropylbenzyl salicylate 94134-93-7 16 3-Imidazol-4-yl-acrylic acidand its ethyl 104-98-3 ester 17 Ethyl 2-cyano-3,3-diphenylacrylate5232-99-5 18 Menthyl o-aminobenzoate or: 134-09-85-methyl-2-(1-methylethyl) 2-aminobenzoate 19 Glyceryl p-aminobenzoateor: 136-44-7 1-glyceryl 4-aminobenzoate 202,2′-Dihyroxy-4-methoxybenzophenone (dioxyben- 131-53-3 zone) 212-Hydroxy-4-methoxy-4-methylbenzophenone 1641-17-4 (mexo-none) 22Triethanolamine salicylate 2174-16-5 23 Dimethoxyphenylglyoxalic acidor: 4732-70-1 sodium 3,4-dimethoxyphenylglyoxalate 243-(4′-sulfo)benzylideneboran-2-one and its 56039-58-8 salts 254-tert-butyl-4′-methoxydibenzoylmethane 70356-09-1 263-(4-Methylbenzylidene)camphor 36861-47-9

In addition, the cosmetic and dermatological preparations according tothe invention can advantageously comprise further inorganic pigmentsbased on metal oxides and/or other metal compounds which are insolubleor virtually insoluble in water, in particular the oxides of iron (e.g.Fe₂O₃), zirconium (ZrO₂), silicon (SiO₂), manganese (e.g. MnO), aluminum(Al₂O₃), cerium (e.g. Ce₂O₃), mixed oxides of the corresponding metals,and admixtures of such oxides.

For the purposes of the present invention, it is particularlyadvantageous, but not obligatory, for the inorganic pigments to bepresent in hydrophobic form, i.e. to have been surface-treated to repelwater. This surface treatment can involve providing the pigments with athin hydrophobic layer in a manner known per se, as described in DE-A-3314 742.

To protect human hair against UV rays, the sunscreen combinations to beused according to the invention can be incorporated into shampoos,lotions, gels, hairsprays, aerosol foam creams or emulsions inconcentrations of from 0.1 to 10% by weight, preferably from 1 to 7% byweight. The respective formulations can be used, inter alia, forwashing, coloring and for styling the hair.

The sunscreen combinations to be used according to the invention arereadily soluble in cosmetic oils and can be easily incorporated intocosmetic formulations. The emulsions prepared with the novel sunscreencombinations are in particular characterized by their high stability,the sunscreen combinations themselves by their high photostability, andthe preparations prepared with the sunscreen combinations by theirpleasant feel on the skin.

The UV filter action of the sunscreen combinations to be used accordingto the invention can also be utilized for stabilizing active ingredientsand auxiliaries in cosmetic and pharmaceutical formulations.

The examples below illustrate the use of the novel sunscreencombinations in more detail.

EXAMPLES Example 1 Standardized Method to Determine Photostability (SunTest)

A 5% by weight alcoholic solution of the sunscreen to be tested isapplied, using an Eppendorf pipette (20 μl), to the milled area on asmall glass plate. Owing to the presence of the alcohol, the solutiondistributes uniformly on the roughened glass surface. The amount appliedcorresponds to the amount of sunscreen required to obtain an average sunprotection factor in sun creams. In the test, 4 small glass plates areirradiated in each case. The evaporation time and the irradiation eachlast for 30 minutes. The glass plates are cooled slightly during theirradiation by a water cooling system located at the base of the suntest apparatus. The temperature inside the sun test apparatus during theirradiation is 40° C. After the samples have been irradiated, they arewashed with ethanol into a dark 50 ml; volumetric flask and measuredusing a photometer. The blank samples are applied in the same way tosmall glass plates and evaporated at room temperature for 30 minutes.Like the other samples, they are washed off with ethanol and diluted to100 ml and measured.

General Procedure for Preparing Emulsions for Cosmetic Purposes

All of the oil-soluble constituents are heated to 85° C. in a stirredvessel. When all of the constituents are molten or are present as liquidphase, the aqueous phase is incorporated with homogenization. Theemulsion is cooled to about 40° C. with stirring, is perfumed andhomogenized, and is then cooled to 25° C. with continuous stirring.

Preparations Example 2 Lip Care Composition

Mass content (% by weight) ad 100 Eucerinum anhydricum 10.00 glycerolFilter combination consisting of 5.00 (I) 8.00 (II) 10.00 TiO₂ 5.00 ZnO₂4.00 castor oil 4.00 pentaerythrityl stearate/caprate/caprylate/adipate3.00 glyceryl stearate SE 2.00 beeswax 2.00 microcrystalline wax 2.00quaternium-18 bentonite 1.50 PEG-45/dodecyl glycol copolymer

Example 3 Lip Care Composition

Mass content (% by weight) ad 100 Eucerinum anhydricum 10.00 glycerolFilter combination consisting of 1.00 (I) 8.00 (II) 4.00 (V) 10.00 TiO₂5.00 ZnO₂ 4.00 castor oil 4.00 pentaerythritylstearate/caprate/caprylate/adipate 3.00 glyceryl stearate SE 2.00beeswax 2.00 microcrystalline wax 2.00 quaternium-18 bentonite 1.50PEG-45/dodecyl glycol copolymer

Example 4 Sunblock Composition Containing Micropigments

Mass content (% by weight) ad 100 water 6.00 PEG-7 hydrogenated castoroil Filter combination consisting of 2.00 (I) 3.00 (V) 10.00 (II) 3.00(X) 6.00 TiO₂ 5.00 mineral oil 5.00 isoamyl p-methoxycinnamate 5.00propylene glycol 3.00 jojoba oil 2.00 PEG-45/dodecyl glycol copolymer1.00 dimethicone 0.50 PEG-40 hydrogenated castor oil 0.50 tocopherylacetate 0.50 phenoxyethanol 0.20 EDTA

Example 5 Sunblock Composition Containing Micropigments

Mass content (% by weight) ad 100 water 6.00 PEG-7 hydrogenated castoroil Filter combination consisting of 2.00 (I) 3.00 (IV) 10.00 (II) 3.00(X) 6.00 TiO₂ 5.00 mineral oil 5.00 isoamyl p-methoxycinnamate 5.00propylene glycol 3.00 jojoba oil 2.00 PEG-45/dodecyl glycol copolymer1.00 dimethicone 0.50 PEG-40 hydrogenated castor oil 0.50 tocopherylacetate 0.50 phenoxyethanol 0.20 EDTA

Example 6 Non-greasy Gel

Mass content (% by weight) ad 100 Filter combination consisting of 2.00(I) 3.00 (VI) 8.00 (II) 1.00 (X) 7.00 TiO₂ 5.00 glycerol 5.00 PEG-25PABA 0.40 acrylate C₁₀-C₃₀ alkyl acrylate crosspolymer 0.30imidazolidinylurea 0.25 hydroxyethylcellulose 0.25 sodium methylparaben0.20 disodium EDTA 0.15 fragrance 0.15 sodium propylparaben 0.10 sodiumhydroxide

Example 7 Non-greasy Gel

Mass content (% by weight) ad 100 water Filter combination consisting of1.00 (I) 4.00 (VI) 8.00 (II) 1.00 (X) 7.00 TiO₂ 5.00 glycerol 5.00PEG-25 PABA 0.40 acrylate C₁₀-C₃₀ alkyl acrylate crosspolymer 0.30imidazolidinylurea 0.25 hydroxyethylcellulose 0.25 sodium methylparaben0.20 disodium EDTA 0.15 fragrance 0.15 sodium propylparaben 0.10 sodiumhydroxide

Example 8 Sun Cream

Mass content (% by weight) ad 100 water Filter combination consisting of2.00 (I) 3.00 (XIV) 8.00 (II) 1.00 (X) 8.00 TiO₂ 5.00 ZnO₂ 6.00 PEG-7hydrogenated castor oil 6.00 mineral oil 5.00 isopropyl palmitate 0.30imidazolidinylurea 3.00 jojoba oil 2.00 PEG-45/dodecyl glycol copolymer0.60 magnesium stearate 0.50 tocopheryl acetate 0.25 methylparaben 0.20disodium EDTA 0.15 propylparaben

Example 9 Sun Cream

Mass content (% by weight) ad 100 water Filter combination consisting of3.00 (I) 3.00 (XI) 8.00 (II) 8.00 TiO₂ 5.00 ZnO₂ 6.00 PEG-7 hydrogenatedcastor oil 6.00 mineral oil 5.00 isopropyl palmitate 0.30imidazolidinylurea 3.00 jojoba oil 2.00 PEG-45/dodecyl glycol copolymer0.60 magnesium stearate 0.50 tocopheryl acetate 0.25 methylparaben 0.20disodium EDTA 0.15 propylparaben

Example 10 Water-resistant Sun Cream

Mass content (% by weight) ad 100 water Filter combination consisting of1.00 (I) 4.00 (IX) 8.00 (II) 2.00 (X) 3.00 TiO₂ 5.00 PEG-7 hydrogenatedcastor oil 5.00 propylene glycol 4.00 isopropyl palmitate 4.00caprylic/capric triglyceride 4.00 glycerol 3.00 jojoba oil 1.50PEG-45/dodecyl glycol copolymer 1.50 dimethicone 0.70 magnesium sulfate0.50 magnesium stearate 0.15 fragrance

Example 11 Water-resistant Sun Cream

Mass content (% by weight) ad 100 water Filter combination consisting of2.00 (I) 5.00 (XII) 2.00 TiO₂ 5.00 PEG-7 hydrogenated castor oil 5.00propylene glycol 4.00 isopropyl palmitate 4.00 caprylic/caprictriglyceride 4.00 glycerol 3.00 jojoba oil 1.50 PEG-45/dodecyl glycolcopolymer 1.50 dimethicone 0.70 magnesium sulfate 0.50 magnesiumstearate 0.15 fragrance

Example 12 Sun Milk

Mass content (% by weight) ad 100 water 10.00 mineral oil 6.00 PEG-7hydrogenated castor oil 5.00 isopropyl palmitate Filter combinationconsisting of 3.00 (I) 5.50 (VIII) 3.00 caprylic/capric triglyceride3.00 jojoba oil 2.00 PEG-45/dodecyl glycol copolymer 0.70 magnesiumsulfate 0.60 magnesium stearate 0.50 tocopheryl acetate 3.00 glycerol0.25 methylparaben 0.15 propylparaben 0.05 tocopherol

Example 13 Sun Milk

Mass content (% by weight) ad 100 water 10.00 mineral oil 6.00 PEG-7hydrogenated castor oil 5.00 isopropyl palmitate Filter combinationconsisting of 1.00 (I) 4.00 (XIV) 3.50 (II) 3.00 caprylic/caprictriglyceride 3.00 jojoba oil 2.00 PEG-45/dodecyl glycol copolymer 0.70magnesium sulfate 0.60 magnesium stearate 0.50 tocopheryl acetate 3.00glycerol 0.25 methylparaben 0.15 propylparaben 0.05 tocopherol

We claim:
 1. A method for protecting human epidermis or human hair fromUV radiation further comprising applying an effective amount of asunscreen combination, further comprising a A) compound absorbingessentially in the UV-A region and B) further compounds absorbing in theUV-A region, in the UV-B region and over both regions,  where theconstituent absorbing in the UV-A region consists of A) effectiveamounts of at least one of the compounds of the formula I

 in which the substituents R¹ to R³, independently of one another, areC₁-C₈-alkyl  and the constituent B) comprises effective amounts of oneor more compounds chosen from the group consisting of Ba)hydroxybenzophenones of the formula II

 in which the substituents, independently of one another, have thefollowing meanings: R⁴ and R⁵ are hydrogen, C₁-C₁₂-alkyl,C₃-C₁₀-cycloalkyl, where the substituents R⁴ and R⁵ may, together withthe nitrogen atom to which they are bonded, form a 5- or 6-membered ringand R⁶ hydrogen, C₁-C₁₂-alkyl, C₃-C₁₀-cycloalkyl; Bb) diarylbutadienesof the formula III

 in which the substituents R⁷ and R⁸, independently of one another, maybe hydrogen, C₁-C₁₂-alkyl or C₃-C₁₀-cycloalkyl, Bc) the compound of theformula IV

Bd) the compound of the formula V

Be) the compound of the formula VI

Bf) the compound of the formula VII

Bg) an organosiloxane benzalmalonate of the formula VIIIa

 in which V₁′ is the group

V₁ is a methyl group or V₁′, or of the formula VIIIb

 in which V₂′ is the group of the structure

V₂ is a methyl group or V₂′ or mixtures of compounds of the formulaeVIIIa and VIIIb, where t is a value up to 100 and u is a value up to 20,with the proviso that u=0 when V₁=V₁′ and/or V₂=V₂′, and u is a valuefrom 1 to 20 when V₁=CH₃ and/or V₂=CH₃, Bh) the compound of the formulaIX

Bi) the compound of the formula X

Bj) the compound of the formula XI

 in which X is hydrogen, sodium, potassium, ammonium ortriethanolammonium, Bk) the compound of the formula XII

and optionally further compounds which absorb in the UV region and whichare known per se for cosmetic and pharmaceutical preparations.
 2. Themethod of claim 1 wherein constituent A) of the formula I is present inamounts of at least 5% by weight, based on the sunscreen combination. 3.A cosmetic or pharmaceutical preparation comprising sunscreencombinations for the protection of the human epidermis or human hairagainst UV light in the range from 280 to 400 nm, which comprises, in acosmetically or pharmaceutically suitable carrier, as photostable UVfilter, an effective amount of sunscreen combinations which have A) acompound absorbing essentially in the UV-A region and B) furthercompounds absorbing in the UV-A region, in the UV-B region and over bothregions,  where the constituent absorbing in the UV-A region consists ofA) effective amounts of the compound of the formula

 and the constituent B) comprises effective amounts of one or morecompounds chosen from the group consisting of Ba) hydroxybenzophenone ofthe formula IIa

Bb) diarylbutadiene of the formula IIIa

Bc) the compound of the formula IV

Bd) the compound of the formula V

Be) the compound of the formula VI

Bf) the compound of the formula VII

Bg) an organosiloxane benzalmalonate of the formula VIIIa

 in which V₁′ is the group

V₁ is a methyl group or V₁′, or of the formula VIIIb

 in which V₂′ is the group of the structure

V₂ is a methyl group or V₂′ or mixtures of compounds of the formulaeVIIIa and VIIIb, where t is a value up to 100 and u is a value up to 20,with the proviso that u=0 when V₁=V₁′ and/or V₂=V₂′, and u is a valuefrom 1 to 20 when V₁=CH₃ and/or V₂=CH₃, Bh) the compound of the formulaIX

Bi) the compound of the formula X

Bj) the compound of the formula XI

 in which X is hydrogen, sodium, potassium, ammonium ortriethanolammonium, Bk) the compound of the formula XII

optionally together with further compounds which absorb in the UV regionand which are known per se for cosmetic and pharmaceutical preparations.4. A cosmetic or pharmaceutical preparation comprising sunscreencombinations as claimed in claim 3, where the sunscreen combinationscomprise the constituent of the formula I in amounts of at least 5% byweight, based on the sunscreen combination.